REFRIGERANT COMPOSITIONS WHICH INCLUDE A SULPHUR COMPOUND

Abstract: Refrigerant compositions are disclosed which include a first component of bis(trifluoromethyl)sulfide, difluoromethyl (trifluoromethyl) sulfide, pentafluoroethyl sulfur pentafluoride, difluoromethyl sulfur pentafluoride or trifluoromethyl sulfur pentafluoride and a second component of difluoromethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2-trifluoroethane, 1,1-difluoroethane, fluoroethane, dimethyl ether, ammonia, fluoromethyl trifluoromethyl ether, trifluoromethyl methyl ether, 1,1,1,2,2-pentafluoropropane, 2-fluoropropane, cyclopropane, bis(difluoromethyl)ether, 1,1,2,2-tetrafluoropropane, 1,1,1,2-tetrafluoropropane, 1-fluoropropane, 1,1,1,3,3-pentafluoropropane, 1,2,2-trifluoropropane, 2,2-difluoropropane, 1,2-difluoropropane, 1,1-difluoropropane, 1-trifluoromethoxy-2,2,2-trifluoroethane or tris(trifluoromethyl)amine.

Description: TTTLE REFRIGERANT COMPOSITIONS WHICH INCLUDE A SULPHUR COMPOUND FIELD OF THE INVENTION This invention relates to refrigerant compositions that include at least one sulphur compound. This invention also relates to binary azeotropic or azeotrope-like compositions that include at least one sulphur compound, said compositions being useful as cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. BACKGROUND OF THE INVENTION Fluorinated hydrocarbons have many uses, one of which is as a refrigerant. Such refrigerants include dichlorodifluoromethane (CFC-12) and chlorodifluoromethane (HCFC-22). In recent years it has been pointed out that certain kinds of fluorinated hydrocarbon refrigerants released into the atmosphere may adversely affect the stratospheric ozone layer. Although this proposition has not yet been completely established, there is a movement toward the control of the use and the production of certain chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) under an international agreement. Accordingly, there is a demand for the development of refrigerants that have a lower ozone depletion potential than existing refrigerants while still achieving an acceptable performance in refrigeration applications. Hydrofluorocarbons (HFCs) have been suggested as replacements for CFCs and HCFCs since HFCs have no chlorine and therefore have zero ozone depletion potential. In refrigeration applications, a refrigerant is often lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the refrigerant may be released to the atmosphere during maintenance procedures on refrigeration equipment. If the refrigerant is not a pure component or an azeotropic or azeotrope-like composition, the refrigerant composition may change when leaked or discharged to the atmosphere from the refrigeration equipment, which cause the refrigerant to become flammable or to have poor refrigeration performance. Accordingly, it is desirable to use as a refrigerant a single fluorinated hydrocarbon or an azeotropic or azeotrope-like composition that includes one or more fluorinated hydrocarbons. Fluorinated hydrocarbons may also be used a cleaning agent or solvent to clean, for example, electronic circuit boards. It is desirable that the cleaning agents be azeotropic or azeotrope-like because in vapor degreasing operations the cleaning agent is generally redistilled and reused for final rinse cleaning. Azeotropic or azeotrope-like compositions that include a fluorinated hydrocarbon are also useful as blowing agents in the manufacture of closed-cell polyurethane, phenolic and thermoplastic foams, as propellants in aerosols, as heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, such as for heat pumps, inert media for polymerization reactions, fluids for removing particulates from metal surfaces, as carrier fluids that may be used, for example, to place a fine film of lubricant on metal parts, or as buffing abrasive agents to remove buffing abrasive compounds from polished surfaces such as metal, as displacement drying agents for removing water, such as from jewelry or metal parts, as resist developers in conventional circuit manufacturing techniques including chlorine-type developing agents, and as strippers for photoresists when used with, for example, a chlorohydrocarbon such as 1,1,1-trichloroethane or trichloroethylene. SUMMARY OF THE INVENTION The present invention relates to the discovery of refrigerant compositions wherein the first component is bis(trifluoromethyl)sulfide, difluoromethyl (trifluoromethyl) sulfide, pentafluoroethyl sulfur pentafluoride, difluoromethyl sulfur pentafluoride or trifluoromethylsulfur pentafluoride and the second component is difluoromethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2- tetrafluoroethane, 1,1,2-trifluoroethane, 1,1-difluoroethane, fluoroethane, dimethyl ether, ammonia, fluoromethyl trifluoromethyl ether, trifluoromethyl methyl ether, 1,1,1,2,2-pentafluoropropane, 2-fluoropropane, cyclopropane, bis(difluoromethyl)ether, 1,1,2,2-tetrafluoropropane, 1,1,1,2-tetrafluoropropane, 2,2- difluoropropane, 1-fluoropropane, 1,1,1,3,3-pentafluoropropane, 1,2,2- trifluoropropane, 2,2-difluoropropane, 1,2-difluoropropane, 1,1-difluoropropane, 1- fluoropropane, l-trifluoromethoxy-2,2,2-trifluoroethane or tris(trifluoromethyl)amine, as well as azeotrope or azeotrope-like compositions of these components. The compositions of the invention are also useful as cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. DETAILED DESCRIPTION The present invention relates to binary compositions of at least one component selected from the following Table 1 and at least one component from the following Table 2. TABLE 1 1. bis (trifluoromethyl) sulfide (116S or CF3SCF3, boiling point = -20.0°C) 2. difluoromethyl (trifluoromethyl) sulfide (125S or CHF2SCF3, boiling point = 1.0°C) 3. pentafluoroethyl sulfur pentafluoride (SF5C2F5, boiling point = 13.5°C) 4. difluoromethyl sulfur pentafluoride (SF5CF2H, boiling point = 5.1°C) 5. trifluoromethylsulfur pentafluoride (SF5CF3, boiling point = -20.4°C) TABLE 2 1. difluoromethane (HFC-32 or CH2F2, boiling point = -51.7°C) 2. 1,1,2,2-tetrafluoroethane (HFC- 134 or CHF2CHF2, boiling point = -19.7°C) 3. 1,1,1,2-tetrafluoroethane (HFC-134a or CF3CH2F, boiling point = -26.5°C) 4. bis(difluoromethyl)ether (134E or CHF2OCHF2, boiling point = 6.2°C) 5. fluoromethyl trifluoromethyl ether (134aE or CH2FOCH3, boiling point = -20.0°C) 6. 1,1,2-trifluoroethane (HFC- 143 or CHF2CH2F, boiling point = 5.0°C) 7. trifluoromethyl methyl ether (143aE or CH3OCF3, boiling point = -24.2°C) 8. 1,1-difluoroethane (HFC- 152a or CHF2CH3, boiling point = -24.7°C) 9. fluoroethane (HFC-161 or CH 2 FCH 3 , boiling point = -37.1°C) 10. l-trifluoromethoxy-2,2,2-trifluoroethane (HFC-236faE or CF3OCH2CF3, boiling point = 5.6°C) 11. 1,1,1,2,2-pentafluoropropane (HFC-245cb or CF3CF2CH3, boiling point = -17.7°C) 12. 1, 1, 1,3,3-pentafluoropropane (HFC-245fa or CF3CH2CHF2, boiling point = 14.0°C) 13. 1,1,2,2-tetrafluoroρroρane (HFC-254cb or CHF2CF2CH3, boiling point = 0,5°C) 14. 1,1,1,2-tetrafluoroρroρane (HFC-254eb or CF3CHFCH3, boiling point = 0.0°C) 15. 1,2,2-trifluoropropane (HFC-263ca of CH3CF2CH2F, boiling point = 18.7°C) 16. 2,2-difluoropropane (HFC-272ca or CH3CF2CH3, boiling point = -0.4°C) 17. 1,2-difluoropropane (HFC-272ea or CH2FCHFCH3, boiling point = 15.0°C) 18. 1,1-difluoropropane (HFC-272fb or CH3CH2CHF2, boiling point = 8.0°C) 19. 2-fluoropropane (HFC-281ea or CH3CHFCH3, boiling point = -9.4°C) 20. 1-fluoroproρane (HFC-281fa or CH2FCH2CH3, boiling point = -2.5°C) 21. ammonia (NH3) 22. cyclopropane 23. dimethyl ether (DME, boiling point = -24.8°C) 24. tris(trifluoromethyl)amine ((CF3)3N, boiling point = -6.5°C) 116S (CAS Reg. No. 371-78-8) has been prepared by the thermal decomposition of CF3C(0)OSCF3 as described by Haas and Oh in Chem. Ber., Vol. 102, pages 77-82 (1969). 125S (CAS Reg. No. 371-72-2) has been prepared by the photolysis of CF2HC(0)OSCF3 as described by Yu et. al. in Inorg. Chem., Vol. 13, pages 484-486 (1974). SF5C2F5 (CAS Reg. No. 354-67-6) has been prepared by electrochemical fluorination of ethyl sulfide in anhydrous hydrogen fluoride as reported by Dresdner in J. Am. Chem. Soc, Vol. 79, pages 69-70 (1957). SF5CF2H (CAS Reg. No. 420-67-7) has been prepared by reaction of methyl mercaptan with fluorine gas as disclosed by Silvey and Cady in U.S. Patent No. 2,697,726 and J. Am. Chem. Soc, Vol. 72, pages 3624-26 (1950). SF5CF3 (CAS Reg. No. 373-80-8) has been prepared by the reaction fo methyl mercaptan with either cobalt trifluoride or fluorine gas as disclosed by Silvey and Cady in US Patent No. 2,697,726 and J. Am. Chem. Soc, Vol. 79, pages 3624-3626 (1950). 134E (CAS Reg. No. 1691-17-4) can be prepared by reaction of antimony trifluoride with CHF2OCHCI2 as disclosed by O'Neill in GB 2,248,617. 134aE (CAS Reg. No. 2261-01-0) has been made by the electrochemical fluorination of methyl 2-methoxypropionate as reported by Berenblit, et. al. Zh. Org. Khim., Vol. 12, pp.767-770 (1976). 143aE (CAS Reg. No. 421-14-7) has been made by the reaction of methyl fluoroformate with sulfur tetrafluoride as reported by Aldrich and Sheppard, J. Am. Chem. Soc, Vol. 29, 11-15 (1964). (CF3)3N (CAS Reg. No. 432-03-1) has been made by electrochemical fluorination of trimethyl amine in anhydrous hydrogen fluoride as disclosed by Kauck and Simons in U. S. Patent 2,616,927. The present invention also relates to the discovery of azeotropic or azeotrope-like compositions of effective amounts of 116S and HFC-32, HFC- 134, HFC-134a, HFC-143, HFC-152a, HFC-161, DME, NH3, 134aE, 143aE, HFC-245cb, HFC-281ea, or cyclopropane; 125S and HFC-32, 134E, HFC- 143, NH3, HFC-254cb, HFC-254eb, HFC-272ca or HFC-281fa; SF 5 C 2 F 5 and HFC-32, HFC-245fa, HFC- 263ca, HFC-272ca, HFC-272ea, HFC-272fb, HFC-281fa, NH3 or DME; SF 5 CF 2 H and 236faE, HFC-245cb, NH3 or (CF 3 )3N; SF5CF3 and HFC-32, HFC-134a, HFC- 152a, 134aE, HFC-161, DME, cyclopropane, 143aE, HFC-245cb, HFC- 143 or NH3 to form an azeotropic or azeotrope-like composition. By "azeotropic" composition is meant a constant boiling liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without compositional change. Constant boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixtures of the same components. By "azeotrope-like" composition is meant a constant boiling, or substantially constant boiling, liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change. It is recognized in the art that a composition is azeotropic or azeotrope-like if, after 50 weight percent of the composition is removed such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than 10 percent, when measured in absolute units. By absolute units, it is meant measurements of pressure and, for example, psia, atmospheres, bars, torr, dynes per square centimeter, millimeters of mercury, inches of water and other equivalent terms well known in the art. Therefore, included in this invention are compositions of effective amounts of 125E and a second component, wherein the second component is NH3, DME, cyclopropane, propane or propylene such that after 50 weight percent of an original composition is evaporated or boiled off to produce a remaining composition, the difference in the vapor pressure between the original composition and the remaining composition is 10 percent or less. Substantially constant boiling, azeotropic or azeotrope-like compositions of this invention comprise the following (except where indicated, all compositions are measured at 25°C): Component Azeotrope-Like Range Preferred Range 116S/HFC-32 19-70/30-81 30-70/30-70 116S/HFC-134 1-99/ 1-99 30-99/ 1-70 116S/HFC-134a 1-99/ 1-99 30-99/ 1-70 116S/HFC-143 51-99/ 1-49 116S/HFC-152a 1-99/ 1-99 40-99/ 1-60 116S/HFC-161 1-79/21-99 50-79/21-50 116S/DME 27-89/11-73 50-89/11-50 II6S/NH3 67-94/ 6-33 116S/HFC-134aE 1-99/ 1-99 30-99/ 1-70 116S/HFC-143aE 1-99/ 1-99 30-99/ 1-70 116S/HFC-245cb 1-99/ 1-99 10-99/ 1-90 116S/HFC-281ea 1-99/ 1-99 50-99/ 1-50 116S/cyclopropane 1-99/ 1-99 50-99/ 1-50 125S/HFC-32 1-53/47-99 125S/HFC-134E 1-99/ 1-99 125S/HFC-143 30-99/ 1-70 40-99/ 1-60 125S/NH 3 48-91/ 9-52 For purposes of thi: intion, "effective amount" is defined as the amount of each component of the .aventive compositions which, when combined, results in the formation of an azeotropic or azeotrope-like composition. This definition includes the amounts of each component, which amounts may vary depending on the pressure applied to the composition so long as the azeotropic or azeotrope-like compositions continue to exist at the different pressures, but with possible different boiling points. Therefore, effective amount includes the amounts, such as may be expressed in weight percentages, of each component of the compositions of the instant invention which form azeotropic or azeotrope-like compositions at temperatures or pressures other than as described herein. For the purposes of this discussion, azeotropic or constant-boiling is intended to mean also essentially azeotropic or essentially-constant boiling. In other words, included within the meaning of these terms are not only the true azeotropes described above, but also other compositions containing the same components in different proportions, which are true azeotropes at other temperatures and pressures, as well as those equivalent compositions which are part of the same azeotropic system and are azeotrope-like in their properties. As is well recognized in this art, there is a range of compositions which contain the same components as the azeotrope, which will not only exhibit essentially equivalent properties for refrigeration and other applications, but which will also exhibit essentially equivalent properties to the true azeotropic composition in terms of constant boiling characteristics or tendency not to segregate or fractionate on boiling. It is possible to characterize, in effect, a constant boiling admixture which may appear under many guises, depending upon the conditions chosen, by any of several criteria: * The composition can be defined as an azeotrope of A, B, C (and D„.) since the very term "azeotrope" is at once both definitive and limitative, and requires that effective amounts of A, B, C (and D.„) for this unique composition of matter which is a constant boiling composition. * It is well known by those skilled in the art, that, at different pressures, the composition of a given azeotrope will vary at least to some degree, and changes in pressure will also change, at least to some degree, the boiling point temperature. Thus, an azeotrope of A, B, C (and D...) represents a unique type of relationship but with a variable composition which depends on temperature and/or pressure. Therefore, compositional ranges, rather than fixed compositions, are often used to define azeotropes. * The composition can be defined as a particular weight percent relationship or mole percent relationship of A, B, C (and D...), while recognizing that such specific values point out only one particular relationship and that in actuality, a series of such relationships, represented by A, B, C (and D...) actually exist for a given azeotrope, varied by the influence of pressure. * An azeotrope of A, B, C (and D„.) can be characterized by defining the compositions as an azeotrope characterized by a boiling point at a given pressure, thus giving identifying characteristics without unduly limiting the scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available. The azeotrope or azeotrope-like compositions of the present invention can be prepared by any convenient method including mixing or combining the desired amounts. A preferred method is to weigh the desired component amounts and thereafter combine them in an appropriate container. Specific examples illustrating the invention are given below. Unless otherwise stated therein, all percentages are by weight. It is to be understood that these examples are merely illustrative and in no way are to be interpreted as limiting the scope of the invention. EXAMPLE 1 Phε • ?. Study A phase study on the following compositions, wherein the composition is varied and the vapor pressures is measured, at a constant temperature of 25°C, shows that the following compositions are azeotropic (all amounts of components are weight percent). Composition Weight percents Vapor pressure, psia (kPa^ 116S/HFC-32 36.7/63.3 284.6 (1962) 116S/HFC-134 53.5/46.5 94.7 (653) 116S/HFC-134a 32.8/67.2 103.2 (712) 116S/HFC-143 81.1/18.9 85.4 (589) 116S/HFC-152a 57.2/42.8 102.4 (706) 116S/HFC-161 48.8/51.2 147.9 (1020) 116S/DME 65.5/34.5 112.8 (778) H6S/NH3 82.8/17.2 211.5 (1458) 116S/134aE 50.9/49.1 79.6 (549) 116S/143aE 41.5/58.5 88.7 (612) 116S/HFC-245cb 72.9/27.1 73.1 (504) 116S/HFC-281ea 97.5/2.5 71.6 (494) 116S/cyclopropane 41.6/58.4 107.5 (741) 125S/HFC-32 8.0/92.0 248.3 (1712) 125S/134E 77.4/22.6 35.2 (243) 125S/HFC-143 60.6/39.4 47.1 (325) Impact of Vapor Leakage on Vapor Pressure at 25°C A vessel is charged with an initial composition at 25°C, and the vapor pressure of the composition is measured. The composition is allowed to leak from the vessel, while the temperature is held constant at 25°C, until 50 weight percent of the initial composition has been removed, at which time the vapor pressure of the composition remaining in the vessel is measured. The results are summarized below. 116S/134aE 50.9/49.1 79.6(549) 79.6(549) 0.0 70.0/30.0 78.7(543) 78.4(541) 0.4 90.0/10.0 75.0(517) 74.4(513) 0.8 99.0/1.0 71.9(496) 71.8(495) 0.1 30.0/70.0 78.7(543) 78.4(541) 0.4 10.0/90.0 75.9(523) 75.6(521) 0.4 1.0/99.0 74.1(511) 74.0(510) 0.1 116S/143aE 41.5/58.5 88.7(612) 88.7(612) 0.0 60.0/40.0 87.6(604) 87.2(601) 0.5 80.0/20.0 83.1(573) 81.4(561) 2.0 99.0/1.0 72.3(498) 72.0(496) 0.4 20.0/80.0 87.4(603) 87.1(601) 0.3 10.0/90.0 86.0(593) 85.6(590) 0.5 1.0/99.0 84.1(580) 84.0(579) 0.1 116S/HFC-245cb 72.9/27.1 73.1(504) 73.1(504) 0.0 90.0/10.0 72.5(500) 72.5(500) 0.0 99.1/1.0 71.6(494) 71.6(494) 0.0 50.0/50.0 72.3(498) 72.2(498) 0.1 30.0/70.0 70.8(488) 70.6(487) 0.3 10.0/90.0 68.7(474) 68.5(472) 0.3 1.0/99.0 67.5(465) 67.5(465) 0.0 116S/HFC-281ea 97.5/2.5 71.6(494) 71.6(494) 0.0 70.0/30.0 66.9(461) 65.2(450) 2.5 50.0/50.0 61.9(427) 58.1(401) 6.1 40.0/60.0 59.3(409) 54.7(377) 7.8 30.0/70.0 56.6(390) 51.9(358) 8.3 20.0/80.0 53.6(370) 49.7(343) 7.3 10.0/90.0 50.5(348) 48.2(332) 4.6 1.0/99.0 47.5(328) 47.2(325) 0.6 99.0/1.0 71.6(494) 71.6(494) 0.0 116S/cyclopropane 41.6/58.4 107.5(741) 107.5(741) 0.0 60.0/40.0 106.6(735) 106.1(732) 0.5 80.0/20.0 101.0(696) 99.8(674) 1.2 90.0/10.0 92.7(639) 87.1(601) 6.0 99.0/1.0 74.7(515) 73.0(503) 2.3 20.0/80.0 106.7(736) 106.6(735) 0.1 SF 5 C 2 F /HFC-263ca The results of this Example show that these compositions are azeotropic or azeotrope-like because when 50 wt.% of an original composition is removed, the vapor pressure of the remaining composition is within about 10% of the vapor pressure of the original composition, at a temperature of 25°C. EXAMPLE 3 Refrigerant Performance The following table shows the performance of the inventive refrigerants. The data are based on the following conditions. Evaporator temperature 45.0°F (7.2°C) Condenser temperature 130.0°F (54.4°C) Subcool temperature 115.0°F (46.1°C) Return gas temperature 65.0°F (18.3°C) Compressor efficiency is 75%. 116S/HFC-32 36.7/63.3 121.6 (838) 438.7(3025) 192.4(89.1) 2.90 398.5(7.0) 116S/HFC-134 53.5/46.5 48.7 (336) 186.6(1287) 164.1(73.4) 3.41 193.7(3.4) 116S/HFC-134a 32.8/67.2 56.1 (387) 215.1(1483) 164.2(73.4) 3.35 218.1(3.8) 116S/HFC-143 81.1/18.9 33.3 (230) 136.1(938) 158.4(70.2) 3.47 141.6(2.5) 116S/HFC-152a 57.2/42.8 54.4 (375) 202.3(1395) 175.9(79.9) 3.45 217.1(3.8) 116S/HFC-161 48.8/51.2 79.1 (545) 276.0(1903) 183.1(83.9) 3.38 294.9(5.2) 116S/DME 65.5/34.5 58.7 (405) 212.0(1462) 170.1(76.7) 3.45 227.6(4.0) II6S/NH3 82.8/17.2 101.3 (698) 375.0(2586) 209.4(98.6) 3.32 399.0(7.0) 116S/134aE 50.0/49.1 42.9 (296) 168.9(1165) 156.5(69.2) 3.36 170.0(3.0) 116S/143aE 41.5/58.5 48.2(332) 183.9(1268) 160.4(71.3) 3.39 116S/HFC-245cb 72.9/27.1 38.9(268) 150.9(1040) 145.3(62.9) 3.29 116S/HFC-281ea 97.5/2.5 40.3(278) 157.3(1085) 149.2(65.1) 3.29 116S/cyclopropane 41.6/58.4 65.7(453) 225.3(1553) 186.5(85.8) 3.57 125S/HFC-32 8.0/92.0 144.6(997) 496.6(3424) 198.7(92.6) 3.16 125S/134E 77.4/22.6 17.8(123) 82.0(565) 162.1(72.3) 3.64 125S/HFC-143 60.6/39.4 17.6(121) 79.0(545) 173.7(78.7) 3.73 125S/NH 3 66.6/33.4 84.6(583) 340.0(2344) 253.3(122.9) 3.38 125S/HFC-254cb 69.0/31.0 18.6(128) 82.4(568) 156.4(69.1) 3.62 125S/HFC-254eb 36.7/63.3 18.9(130) 82.1(566) 155.3(68.5) 3.62 125S/HFC-272ca 61.6/38.4 18.7(129) 80.7(556) 159.3(70.7) 3.66 125S/HFC-281fa 45.1/54.9 20.1(139) 86.1(594) 166.2(74.6) 3.70 SF 5 C 2 F 5 /HFC-32 64.0/36.0 60.9(420) 308.1(2124) 192.4(89.1) 2.93 15.0/85.0 148.0(1020) 504.6(3479) 195.3(90.7) 3.23 1.0/99.0 149.6(1031) 510.5(3520) 199.9(93.3) 3.16 99.0/1.0 15.8(109) 79.1(545) 142.7(61.5) 3.86 SF 5 C 2 F 5 /HFC-245fa 71.8/28.2 11.2(77) 58.4(403) 143.8(62.1) 3.51 57.0(1.0) SF 5 C 2 F 5 /HFC-263ca 1.0/99.0 9.4 (65) 82.6/17.4 10.7 (74) 99.0/1.0 11.5 (79) SF 5 C2F 5 /HFC-272ca 16.5/83.5 18.4 (127) 77.4 (534) 158.8 (70.4) 3.68 86.8 (1.5) SF 5 C 2 F 5 /HFC-272ea 76.3/23.7 11.7 (81) 59.4 (410) 149.7 (65.4) 3.59 60.4 (1.1) SF 5 C2F 5 /HFC-272fb 56.5/43.5 13.6 (94) 65.2 (450) 156.2 (69.0) 3.64 69.1 (1.2) SF 5 C 2 F 5 /HFC-281fa 6.9/93.1 20.5 (141) 86.4 (596) 168.7 (75.9) 3.71 98.4 (1.7) SF5C2F5/NH3 68.5/31.5 87.5 (603) 380.7 (2625) 255.8 (124.3) 3.1 378.6 (6.7) SF 5 CF 2 H/HFC-245cb 95.0/5.0 17.5 (121) 88.1 (607) 162.7 (72.6) 3.63 90.9 (1.6) 66.0/34.0 24.2 (167) 110.8 (764) 154.2 (67.9) 3.49 112.3 (2.0) 23.1/76.9 33.0 (228) 132.0 (910) 143.3 (61.8) 3.34 131.2 (2.3) 1.0/99.0 36.1 (249) 137.0 (945) 139.1 (59.5) 3.31 135.9 (2.4) SF 5 CF 2 H/(CF 3 )3N 95.0/5.0 17.7 (122) 88.9 (613) 161.9 (72.2) 3.67 92.6 (1.6) 71.0/29.0 22.4 (154) 108.7 (749) 153.9 (67.7) 3.44 105.6 (1.9) 27.2/72.8 28.7 (198) 123.5 (852) 138.2 (59.0) 3.15 111.2 (2.0) 1.0/99.0 25.6 (177) 111.4 (768) 136.8 (58.2) 3.02 95.2 (1.7) SF 5 CF 2 H/HFC-236faE 99.0/1.0 16.2 (112) 83.4 (575) 164.4 (73.6) 3.61 85.2 (1.5) 81.5/18.5 16.9 (117) 84.9 (585) 158.9 (70.5) 3.58 86.2 (1.5) 1.0/99.0 15.7 (108) 74.6 (514) 142.2 (61.2) 3.46 73.6 (1.3) SF5CF2H/NH3 66.8/33.2 82.5 (569) 346.2 (2387) 265.1 (129.5) 3.34 380.5 (6.7) SF5CF3/HFC-32 95.0/5.0 61.4(423) 252.0 (1737) " 162.6 (72.6) 73.0/27.0 106.5(734) 411.3(2836) 182.1(83.4) 40.6/59.4 146.8(1012) 503.5(3472) 189.9(87.7) 19.0/81.0 151.4(1044) 514.1 (3545) 195.4(90.8) 5.0/95.0 150.2(1036) 512.2(3532) 199.1(92.8) SF 5 CF 3 /HFC-134a 99.0/1.0 45.8(316) 193.7(1336) 155.3(68.5) 39.4/60.6 53.6(370) 213.4(1471) 166.1(74.5) 1.0/99.0 54.5(376) 214.1(1478) 170.8(77.1) SF 5 CF 3 /HFC-152a 99.0/1.0 45.9(316) 193.8(1336) 155.9(68.8) 65.5/34.5 51.2(353) 202.3(1395) 177.3(80.7) 1.0/99.0 50.8(350) 193.4(1333) 203.9(95.5) SF 5 CF 3 /134aE 99.0/1.0 45.5(314) 192.4(1327) 155.2(68.4) 80.1/19.9 43.9(303) 183.8(1207) 157.4(69.7) 1.0/99.0 41.8(288) 167.7(1156) 163.9(73.3) SF5CF3/HFC-I6I 95.0/5.0 51.7(356) 212.6(1466) 160.8(71.6) 85.0/15.0 60.7(419) 238.4(1644) 169.3(76.3) 53.2/46.8 74.4(513) 271.0(1868) 186.1(85.6) 1.0/99.0 79.7(550) 279.6(1928) 201.0(93.9) SF5CF3/DME 99.0/1.0 46.4(320) 195.4(1347) 156.1(68.9) 71.9/28.1 53.9(372) 207.5(1431) 172.7(78.2) 1.0/99.0 48.4(334) 182.3(1257) 193.2(89.6) SF5CF3/cyclopropane 1.0/99.0 62.6(432) 214.9(1482) 200.2(93.4) 44.6/55.4 62.7(432) 221.3(1526) 189.1(87.3) 99.0/1.0 46.7(322) 195.8(1350) 156.3(69.1) SF 5 CF 3 /143aE 99.0/1.0 45.6(314) 192.8(1329) 155.3(68.5) 56.3/43.7 46.9(323) 187.7(1294) 161.6(72.0) 1.0/99.0 47.9(330) 183.9(1268) 167.0(75.0) SF 5 CF 3 /HFC-245cb 99.0/1.0 45.4 (313) 192.1 (1324) 154.9 (68.3) 3.17 175.2 (3.1) 83.8/16.2 43.0 (296) 178.5 (1231) 151.4 (66.3) 3.22 166.9 (2.9) 1.0/99.0 36.2 (250) 137.5 (948) 139.0 (59.4) 3.30 136.3 (2.4) SF5CF3/HFC-I43 87.1/12.9 34.9 (241) 154.9 (1068) 162.3 (72.4) 3.41 153.8 (2.7) SF5CF3/NH3 13.8/86.2 105.6 (728) 351.2 (2421) 193.1 (89.5) 3.83 437.1 (7.7) The novel compositions of this invention, including the azeotropic or azeotrope-like compositions, may be used to produce refrigeration by condensing the compositions and thereafter evaporating the condensate in the vicinity of a body to be cooled. The novel compositions may also be used to produce heat by condensing the refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant. In addition to refrigeration applications, the novel constant boiling or substantially constant boiling compositions of the invention are also useful as aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, expansion agents for polyolefins and polyurethanes and power cycle working fluids. ADDITIONAL COMPOUNDS Other components, such as aliphatic hydrocarbons having a boiling point of -60 to + 30°C, hydrofluorocarbonalkanes having a boiling point of -60 to +30°C, hydrofluoropropanes having a boiling point of between -60 to +30°C, hydrocarbon esters having a boiling point between -60 to +30°C, hydrochloro- fluorocarbons having a boiling point between -60 to +30°C, hydrofluorocarbons having a boiling point of -60 to +30°C, hydrochlorocarbons having a boiling point between -60 to +30°C, chlorocarbons and perfluorinated compounds, can be added to the azeotropic or azeotrope-like compositions described above. Optionally, non-refrigerant additives may be added to the refrigerant compositions disclosed herein. By "non-refrigerant additives" is meant additives that are not refrigerants but which may be added to refrigerant compositions for a variety of purposes. Examples of non-refrigerant additives include lubricants, corrosion inhibitors, stabilizers, and dyes. Preferred lubricants include esters having a molecular weight greater than 250. If the compositions of the invention are used as cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, or displacement drying agents, additives appropriate to those uses may be added to the compositions of the invention.

Claims: CLAIMS 1. A refrigerant composition comprising a first component selected from the group consisting of bis(trifluoromethyl)sulfide, difluoromethyl (trifluoromethyl) sulfide, pentafluoroethyl sulfur pentafluoride, difluoromethyl sulfur pentafluoride or trifluoromethylsulfur pentafluoride and a second component selected from the group consisting of difluoromethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2-trifluoroethane, 1,1-difluoroethane, fluoroethane, dimethyl ether, ammonia, fluoromethyl trifluoromethyl ether, trifluoromethyl methyl ether, 1,1,1,2,2-pentafluoropropane, 2-fluoropropane, cyclopropane, bis(difluoromethyl)ether, 1, 1,2,2-tetrafluoropropane, 1, 1, 1,2-tetrafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,2,2-trifluoropropane, 2,2-difluoropropane, 1,2- difluoropropane, 1,1-difluoropropane, 1-fluoropropane, l-trifluoromethoxy-2,2,2- trifluoroethane or tris(trifluoromethyl)amine. 2. Effective amounts of bis(trifluoromethyl)sulfide and difluoromethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1- trifluoroethane, 1,1-difluoroethane, fluoroethane, dimethyl ether, ammonia, fluoromethyl trifluoromethyl ether, trifluoromethyl methyl ether, 1,1,1,2,2- pentafluoropropane, 2-fluoropropane, or cyclopropane; difluoromethyl (trifluoromethyl) sulfide and difluoromethane, bis(difluoromethyl)ether, 1,1,1- trifluoroethane, ammonia, 1,1,2,2-tetrafluoropropane, 1,1,1,2-tetrafluoropropane, 2,2-difluoropropane or 1-fluoropropane; pentafluoroethyl sulfur pentafluoride and difluoromethane, 1,1,1,3,3-pentafluoropropane, 1,2,2-trifluoropropane, 2,2- difluoropropane, 1,2-difluoropropane, 1,1-difluoropropane, 1-fluoropropane, ammonia or dimethyl ether; difluoromethyl sulfur pentafluoride and 1- trifluoromethoxy-2,2,2-trifluoroethane, 1,1,1,2,2-pentafluoropropane, ammonia or tris(trifluoromethyl)amine; trifluoromethylsulfur pentafluoride and difluoromethane, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, fluoromethyl trifluoromethyl ether, fluoroethane, dimethyl ether, cyclopropane, trifluoromethyl methyl ether, 1,1,1,2,2-pentafluoropropane, 1,1,1-trifluoroethane or ammonia to form an azeotropic or azeotrope-like composition at 25°C.

Inventors: MINOR BARBARA HAVILAND, MINOR, BARBARA, HAVILAND
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1994
Main classification: C09K5
IPC codes: A62D1, C07C19, C07C43, C07C211, C07C323, C09K3, C09K5, C11D7